Textile laundering composition comprising a self-crosslinking cationic polymer

ABSTRACT

A process for the treatment of non-keratinaceous textiles, preferably cellulosic fibers, which comprises the step of treating the textiles with a composition which comprises: a self-crosslinking polymer and a nucleophilic species (preferably a polymer comprising at least one protected thiol group), and a textile compatible carrier. Under domestic washing conditions the polymer forms reactive thiol groups which are capable of causing covalent cross-linking with the polymer. Preferably, the thiol group is protected as an isothiouronium group.

FIELD OF THE INVENTION

This invention relates to fabric care compositions, including detergentcompositions and laundry rinse compositions. The invention also relatesto methods of treating fabric using the compositions of the invention.

BACKGROUND AND PRIOR ART

The appearance of coloured fabrics, e.g., clothing, bedding, householdfabrics like table linens is one of the areas of concern to consumers.Indeed, upon typical consumer's uses of the fabrics such as wearing,washing, rinsing and/or tumble-drying of fabrics, lead to changes infabric appearance, which is at least partly due to loss of colour shadeintensity, fidelity and color definition.

Such a problem of colour loss is even more acute in laundry treatmentafter multiwash cycles, especially for dark colours, such as blacks,reds, blues, and greens.

Several mechanisms have been speculated upon for colour loss and variousmeans have been proposed to prevent or reduce the extent of the loss ortransfer of colour. For example, colour fixatives, known in the dyeingindustry have been proposed, as have agents (such as PVP) to hold colourmaterials in solution to prevent re-deposition or to prevent abrasionbetween fibers. It has also been suggested to add bleaching agents towash liquor to bleach any dye that enters solution.

One cause of colour loss is the use of an inappropriate detergentcomposition. Thus, many manufacturers produce ‘colour care’ formulationsthat do not contain bleaches. Despite this, colour damage remains asignificant problem in the eyes of consumers.

WO 00/15746 (P&G), filed 15^(th), September 1998, published 23^(rd)March 2000, discloses fabric care compositions, which comprise lowmolecular weight polyamines for colour care. It is believed that thepolyamines intercept peroxygen bleaching. A dye fixative may also bepresent in the compositions disclosed, as may an ‘abrasion reducingpolymer’ such as the N-heterocyclic polymer PVP (see examples 50–53 intable XII).

In order to overcome these problems it has also been proposed to useself cross-linking agents, to treat the fabric. These are believed toform a protective matrix around the fibers of the fabric, which reducesfiber damage. It is believed that this structure restricts relativemovement of the textile fibers and consequently reduces damage to thetextile fibers during the laundering process. It is also believed thatthis reduces pilling and provides shrink resistance.

It is further believed that the structure prevents apparent colour lossby retarding damage to the fibers leading to a rough fiber surface whichwould give the appearance of colour lose due to a modification of themanner in which light is scattered from the fiber surface.

Laundry detergent compositions containing reactive polyamide-polyaminefabric treatment agents are known. The compositions are claimed toimpart improved overall appearance to fabrics laundered using thedetergent compositions, in terms of surface appearance properties suchas pill/fuzz reduction and anti-fading. Other cationic selfcross-linking agents are known.

Polyamine epichlorohydrin resins (PAE) are effective self cross-linkingagents, which is known to reduce fiber damage. However under certaincircumstances use of PAE can lead to changes in the appearance of dyedfabrics as regards their colour. There is a need to overcome thisproblem.

WO 98/12295 (P&G: published 1988) discloses the combination of dyefixing agents and amino-functional polymers to improve the colourappearance of laundered fabrics especially after multi-wash cycles. Onepossible mechanism of action is that the dye fixative locks the dyestuffto the surface preventing colour loss, while the amino functionalpolymer prevents bleaches having a detrimental effect on dyes. There isno suggestion in this document that there is any reaction between theamini-functional material and the dye fixative.

BRIEF DESCRIPTION OF THE INVENTION

The present invention is based on the finding that reaction of acationic self-crosslinking agent with a nucleophile significantlyreduces the tendency of the self-crosslinking agent to cause colourdamage. Surprisingly, this also improves the efficiency of theself-crosslinking reaction enabling it to be performed at lowertemperatures. These lower temperatures further reduce the extent offabric damage.

It is believed that the propensity of the cationic self-crosslinkingagents (such as PAE) to change the colour of dyes is in part due topresence of a cationic charge on the molecule. It is believed that theself-crosslinking agents are both attracted to anionic charges presenton many dyestuffs, leading to a hue change, and that these materials canalso bind dyes and soil from solution leading to a loss of colourdefinition.

According to the present invention, there is provided a launderingprocess for the treatment of non-keratinaceous textiles, which comprisesthe step of treating the textiles with a composition comprising:

-   a) a self-crosslinking cationic polymer,-   b) a nucleophilic species capable of reacting with the polymer (a),    said nucleophilic species being protected by a group which is labile    under the conditions of pH and temperature in the laundering    process, and,-   c) a textile compatible carrier.

The present invention further provides a composition for this treatmentwhich comprises:

-   a) a self-crosslinking cationic polymer-   b) a nucleophilic species capable of reacting with polymer (a), said    nucleophilic species being protected by a group which is labile    under the conditions of pH and temperature in the laundering    process, and,-   c) a textile compatible carrier.

We believe that reaction with a nucleophile reduces the cationic chargeon the self-crosslinking agent and this both reduced the tendency tocause colour damage and other negatives caused by soil and dye binding,and, improves the reaction rate by forming a more reactive species.

DETAILED DESCRIPTION OF THE INVENTION

The textiles, which are intended to be treated in the present invention,preferably comprise cellulosic fibres, preferably from 1% to 100%cellulosic fibres (more preferably 5% to 100% cellulosic fibres, mostpreferably 40% to 100%). When the textile contains less than 100%cellulosic fibres, the balance comprises other fibres or blends offibres suitable for use in garments such as polyester, for example.Preferably, the cellulosic fibres are of cotton or regenerated cellulosesuch as viscose.

The laundering processes of the present invention include the largescale and small scale (e.g. domestic) cleaning of textiles. Preferably,the processes are domestic.

Self-crosslinking Cationic Polymers

Preferably, the reactive cationic polymer is an amine- oramide-epichlorohydrin resin or derivative thereof. Preferably thesecationic polymers have a weight average mean molecular weight of from300 to 1,000,000 Dalton.

The preferred epichlorohydrin resins of the invention are sometimesreferred to as amine-epichlorohydrin resins andpolyamine-epichlorohydrin (PAE) resins (the two terms being usedsynonymously) although these terms encompass both the amine and amideresins of the invention and their derivatives. The resins may also havea mixture of amine and amide groups.

The amine- or amide-epichlorohydrin resins preferably have one or morefunctional groups capable of forming azetidinium groups and/or one ormore azetidinium functional groups. These have the structure givenbelow:

Alternatively, or additionally, the resins may have one or morefunctional groups that contain epoxide groups or derivatives thereofe.g. Kymene™ 450 (ex Hercules)

Suitable polyamine-epichlorohydrin (PAE) resins include those describedin “Wet Strength Resins and Their Application”, pp 16–36, ed. LL Chan,Tappi Press, Atlanta, 1994. Suitable resins can be identified byselecting those resins, which impart increased wet strength to paper,after treatment, in a relatively simple test.

Amine- or amide-epichlorohydrin resins having an epoxide functionalgroup or derivative thereof are suitable for use according to theinvention.

A particularly preferred class of amine- or amide-epichlorohydrin resinsfor use in the invention are secondary amine- or amide-based azetidiniumresins, for example those resins derived from a polyalkylene polyaminee.g. diethylenetriamine (DETA), a polycarboxylic acid e.g. adipic acidor other dicarboxylic acids, and epichlorohydrin.

Other polyamines or polyamides can also be advantageously used in thepreparation of suitable PAE resins.

Another preferred class of amine-epichlorohydrin resins suitable for usein the invention is that having an epoxide functional group orderivative thereof e.g. a chlorohydrin group.

The resin may be a PDAA-epichlorohydrin resin or a PMDAA-epichlorohydrinresin. PDAA is poly(diallylamine) and PMDAA is poly(methyldiallyl(amine)).

The resin is preferably present in the product in a sufficient quantityto give an amount of 0.0005–5% by weight on the fabric based on theweight of fabric (owf), more preferably 0.001–2% owf. The amount of theresin in the composition required to achieve the above % by weight onfabric will typically be in the range 0.01% to 35% by weight, preferably0.1% to 13.5% by weight.

Examples of suitable azetidinium containing materials are thoseavailable as the ‘Hercosett’™ and ‘Listrilan’™ polymers. These arebelieved to be amine or amide-epichlorohydrin resin having one or moreazetidinium functional groups.

Nucleophile Species Capable of Reacting with the Polymer

Preferred nucleophilic species are those containing reactive thiol,amino (both primary and secondary), thiosulphate, phosphonate, or somecarboxylates. These species can be polymers or can be of relatively lowmolecular weight.

Those having thiol, amino or thiosulphate reactive species are preferreddue to their ease of reaction. Those having phosphonate or carboxylatereactive species are less preferred as at lower temperatures they have atendency merely to complex through ionic interactions rather thancross-link through the formation of a covalent bond.

The nucleophile is protected as self-crosslinking reactions wouldotherwise occur between the nucleophilic species.

Particularly preferred nucleophile species are those having a protectedthiol group with a suitably labile leaving group. It is most preferablethat the protected thiol group comprises an isothiouronium group.

Use of an isothiouronium containing polymer, or other thiol groupprotected by another suitably labile leaving group, in a compositionwhich further comprises a textile compatible carrier is believed toreduce fiber damage and/or improve the dimensional stability ofcellulosic textiles following domestic laundry. For illustrativepurposes, the compositions of the present invention will be furtherdescribed below with reference to those comprising at least one polymercomprising at least one isothiouronium group.

The isothiouronium group fulfils the requirements of a suitableprotecting group as it is labile under conditions of pH and temperaturefound in domestic laundry. Typical conditions encountered are a pH from8 to 11 and a temperature of 10 to 80 Celsius. Slightly highertemperatures are encountered under some ironing and domestic dryingconditions. It is preferable that the protecting group is sufficientlylabile that it leaves when the polymer is exposed to a pH of above 8 ata temperature of below 50 Celsius.

Isothiouronium salts are advantageous in that they are can heat cured,for example by a domestic ironing or tumble drying procedure. If used,heat curing is preferably carried out at a temperature in the range offrom 50 to 100° C., more preferably from 80 to 100° C.

The polymer is preferably present in the textile care composition in asufficient quantity to give an amount of 0.0005% to 5% by weight on thetextile based on the weight of the textile, more preferably 0.001% to 2%by weight on textile.

Preferably, the polymers have a weight average mean molecular weight offrom 300 to 1,000,000 Dalton.

As explained above, the polymers of the invention undergo eliminationunder mildly alkaline conditions, such as those encountered during adomestic laundering process, to produce thiol intermediates. These canthen react as nucleophiles with the self cross-linking polymer (forexample PAE). This two-component reaction has two advantages. Firstly,the reaction proceeds quickly and at lower temperatures due to the easeof reactivity between the components (for example between PAE and athiol). Secondly, the product obtained does not suffer the disadvantageof a residual positive charge which can cause dye damage and assist inthe adherence of soils and dyestuffs from solution.

Preferably, the molecular weight of the thiol-containing polymers usedis such that any unpleasant odor component associated with the thiolintermediate is not sufficiently volatile to affect the efficacy of thetextile care composition.

As will be illustrated hereafter the backbone of the polymer can takeseveral forms. Preferred polymers according to the invention are basedon either polypropylene oxide or polyethyleneimine. Polypropylenepolymers are preferred as they give a softer feel to treated fabrics.

Preferably, the protected thiol polymers used in the compositions of theinvention have two or more reactive end groups. It had been foundpreferable to employ polymers with three or more reactive end groups.

Formula (I) below shows an illustrative protected-thiol polymer based onpolypropylene oxide.

As can be seen from the illustrative Formula (I) the molecules of thatseries of embodiments contain a number of linked backbones (in this casethree), a linker group towards the free end of the backbone and theprotected thiol group at the terminal. As will be understood from theforgoing, at high pH the urea leaves the protected thiol group.

While it is preferred that the protected thiol is in a terminal position(as in Formula I above) it is possible to produce polymers in which theprotected thiol is non-terminal (as in Formula II, below).

By way of example, Formula II shows how a protected thiol group may beintroduced into a polyethyleneimine by reaction with chloropropionylchloride followed by reaction of the product with thiourea.

As noted above, these components are used together with aself-crosslinking polymer (for example PAE). At alkaline pH, such as aretypical washing conditions, the thiourea structure decomposes with theloss of the labile urea from the protected thiol. This exposes thereactive thiol group. The thiol then easily reacts with, for example theazetidinium group, forming a mono-sulphide cross-linked structure.

Details of other commercially available polymers which can act asbackbones for the isothiouronium containing polymers are as follows:

Dethylenetriamine/adipic Acid Polymer Derived Nucleophiles:

Polymers based on diethylenetriamine/adipic acid are reacted withchloropropionyl chloride and thiourea to give isothiouronium-containingpolymers, as shown in the figure below.

As with the illustrative embodiments discussed above, these polymerslose the protective group under the conditions of the wash and theexposed thiol group can react with the self-crosslinking polymer.

Nucleophiles Derived from Amino Functional Dendrimers:

Embodiments of the invention are not limited to polymers having arelatively small number of terminal or mid chain protected groups.Dendrimers containing a multiplicity of amino groups can be reacted withchloro-acetyl chloride and thiourea to give suitable isothiouroniumpolymers. Suitable starting molecules include Lupasols,™ (ex-BASF)StarBurst™ (ex-Dow) or DAB-Am™ (ex-DSM) molecules.

The backbone of the nucleophile-bearing polymer can be a carbohydrate orcarbohydrate derivative as shown below.

Nucleophiles Derived from Chitosan:

Chitosan can be reacted with chloropropionyl chloride and then withthiourea to give a water soluble cationic product having pendantisothiouronium groups.

It is not necessary to synthesize the polymers from amines as describedabove.

Nucleophiles Derived from Poly(Vinyl Alcohol):

PVA can be reacted with chloropropionyl chloride and then reacted withthiourea to give a cationic water-soluble polymer with a labile urearesidue. As in the previous descriptions the labile urea may bemid-chain or terminal.

Non-polymeric Nucleophile Species:

It is known to add chelating agents to laundry compositions to reducecolor shifting, especially for the reduction of bluing of direct reddyes when tap water containing dissolved metals such as iron, copper,and the like is used.

Chelating agents suitable for use herein can be selected from the groupconsisting of amino-carboxylates, imino-disuccinates,hydroxy-carboxylates (especially citrates), phosphonates (especially theamino-phosphonates), polyfunctionally-substituted aromatic chelatingagents, phosphates, and mixtures thereof.

Without intending to be bound by theory, it is believed that a part ofthe benefit of these materials is due in part to their exceptionalability to remove iron, copper and manganese ions from washing solutionsby formation of soluble chelates. Commercial chelating agents for useherein include imino-disuccinate TP© from Bayer; DEQUEST™ series, andchelants from Monsanto, DuPont, and Nalco, Inc.

Amino-carboxylates useful as optional chelating agents are furtherillustrated by ethylene-diaminetetracetates,N-hydroxyethyl-ethylene-diaminetriacetates, nitrilotriacetates,ethylene-diamine tetraproprionates, triethylene-tetraamine-hexacetates,diethylene-triamine-pentaacetates, and ethanol-diglycines, alkali metal,ammonium, and substituted ammonium salts thereof.Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044 issued May 21,1974, to Connor et al. and U.S. Pat. No. 6,099,587 issued Aug. 8, 2000to Scialla et al.; both of which are here incorporated by references forfurther useful examples.

Amino-phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and include theethylene-diaminetetrakis (methylene-phosphonates) and thediethylene-triaminepentakis (methylene-phosphonates). If utilized,chelating agents or transition-metal-selective sequestrants willpreferably comprise from about 0.001% to about 10%, more preferably fromabout 0.05% to about 1% by weight of the compositions herein.

Carboxymethyloxy succinates, and alkali metal, ammonium, substitutedammonium and alkanolamine Salts thereof are also suitable for use aschelating agents in the composition of the invention. See U.S. Pat. No.3,692,685, issued Sep. 19, 1972 to Lamberti et al., which is hereincorporated by reference.

Textile Compatible Carriers

In the context of the present invention the term “textile compatiblecarrier” is a component which can assist in the interaction of the firstcomponent with the textile. The carrier can also provide benefits inaddition to those provided by the first component e.g. softening,cleaning etc. The carrier may be a water or a detergent-active compoundor a textile softener or conditioning compound or other suitabledetergent or textile treatment agent.

If the composition of the invention is to be used in a laundry processas part of a conventional textile treatment product, such as a detergentcomposition, the textile-compatible carrier will typically be adetergent-active compound. Whereas, if the textile treatment product isa rinse conditioner, the textile-compatible carrier will be a textilesoftening and/or conditioning compound.

If the composition of the invention is to be used before, or after, thelaundry process it may be in the form of a spray or foaming product.

The polymer is preferably used to treat the textile in the rinse cycleof a laundering process. The rinse cycle preferably follows thetreatment of the textile with a detergent composition.

Detergent Active Compounds As Carriers:

If the composition of the present invention is in the form of adetergent composition, the textile-compatible carrier may be chosen fromsoap and non-soap anionic, cationic, nonionic, amphoteric andzwitterionic detergent active compounds, and mixtures thereof.

Many suitable detergent active compounds are available and are fullydescribed in the literature, for example, in “Surface-Active Agents andDetergents”, Volumes I and II, by Schwartz, Perry and Berch.

The preferred textile-compatible carriers that can be used are soaps andsynthetic non-soap anionic and nonionic compounds.

Anionic surfactants are well-known to those skilled in the art. Examplesinclude alkylbenzene sulphonates, particularly linear alkylbenzenesulphonates having an alkyl chain length of C₈–C₁₅; primary andsecondary alkylsulphates, particularly C₈–C₁₅ primary alkyl sulphates;alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium saltsare generally preferred.

Nonionic surfactants that may be used include the primary and secondaryalcohol ethoxylates, especially the C₈–C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀–C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

Cationic surfactants that may be used include quaternary ammonium saltsof the general formula R₁R₂R₃R₄N⁺X⁻ wherein the R groups areindependently hydrocarbyl chains of C₁–C₂₂ length, typically alkyl,hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation(for example, compounds in which R₁ is a C₈–C₂₂ alkyl group, preferablya C₈–C₁₀ or C₁₂–C₁₄ alkyl group, R₂ is a methyl group, and R₃ and R₄,which may be the same or different, are methyl or hydroxyethyl groups);and cationic esters (for example, choline esters) and pyridinium salts.

The total quantity of detergent surfactant in the composition issuitably from 0.1 to 60 wt % e.g. 0.5–55 wt %, such as 5–50wt %.

Preferably, the quantity of anionic surfactant (when present) is in therange of from 1 to 50% by weight of the total composition. Morepreferably, the quantity of anionic surfactant is in the range of from 3to 35% by weight, e.g. 5 to 30% by weight.

Preferably, the quantity of nonionic surfactant when present is in therange of from 2 to 25% by weight, more preferably from 5 to 20% byweight.

Amphoteric surfactants may also be used, for example amine oxides orbetaines.

Builders:

The compositions may suitably contain from 10 to 70%, preferably from 15to 70% by weight, of detergency builder. Preferably, the quantity ofbuilder is in the range of from 15 to 50% by weight.

The detergent composition may contain as builder a crystallinealuminosilicate, preferably an alkali metal aluminosilicate, morepreferably a sodium aluminosilicate.

The aluminosilicate may generally be incorporated in amounts of from 10to 70% by weight (anhydrous basis), preferably from 25 to 50%.Aluminosilicates are materials having the general formula:0.8–1.5 M₂O.Al₂O₃.0.8–6 SiO₂where M is a monovalent cation, preferably sodium. These materialscontain some bound water and are required to have a calcium ion exchangecapacity of at least 50 mg CaO/g. The preferred sodium aluminosilicatescontain 1.5–3.5 SiO₂ units in the formula above. They can be preparedreadily by reaction between sodium silicate and sodium aluminate, asamply described in the literature.Textile Softening and/or Conditioner Compounds As Carriers:

If the composition of the present invention is in the form of a textileconditioner composition, the textile-compatible carrier will be atextile softening and/or conditioning compound (hereinafter referred toas “textile softening compound”), which may be a cationic or nonioniccompound.

The softening and/or conditioning compounds may be water insolublequaternary ammonium compounds. The compounds may be present in amountsof up to 8% by weight (based on the total amount of the composition) inwhich case the compositions are considered dilute, or at levels from 8%to about 50% by weight, in which case the compositions are consideredconcentrates.

Compositions suitable for delivery during the rinse cycle may also bedelivered to the textile in the tumble dryer if used in a suitable form.Thus, another product form is a composition (for example, a paste)suitable for coating onto, and delivery from, a substrate e.g. aflexible sheet or sponge or a suitable dispenser during a tumble dryercycle.

Suitable cationic textile softening compounds are substantiallywater-insoluble quaternary ammonium materials comprising a single alkylor alkenyl long chain having an average chain length greater than orequal to C₂₀. More preferably, softening compounds comprise a polar headgroup and two alkyl or alkenyl chains having an average chain lengthgreater than or equal to C₁₄. Preferably the textile softening compoundshave two, long-chain, alkyl or alkenyl chains each having an averagechain length greater than or equal to C₁₆.

Most preferably at least 50% of the long chain alkyl or alkenyl groupshave a chain length of C₁₈ or above. It is preferred if the long chainalkyl or alkenyl groups of the textile softening compound arepredominantly linear.

Quaternary ammonium compounds having two long-chain aliphatic groups,for example, distearyldimethyl ammonium chloride and di(hardened tallowalkyl) dimethyl ammonium chloride, are widely used in commerciallyavailable rinse conditioner compositions. Other examples of thesecationic compounds are to be found in “Surface-Active Agents andDetergents”, Volumes I and II, by Schwartz, Perry and Berch. Any of theconventional types of such compounds may be used in the compositions ofthe present invention.

The textile softening compounds are preferably compounds that provideexcellent softening, and are characterised by a chain melting Lβ to Lαtransition temperature greater than 25° C., preferably greater than 35°C., most preferably greater than 45° C. This Lβ to Lα transition can bemeasured by DSC as defined in “Handbook of Lipid Bilayers”, D Marsh, CRCPress, Boca Raton, Fla., 1990 (pages 137 and 337).

Substantially water-insoluble textile softening compounds are defined astextile softening compounds having a solubility of less than 1×10⁻³ wt %in demineralised water at 20° C. Preferably the textile softeningcompounds have a solubility of less than 1×10⁻⁴ wt %, more preferablyless than 1×10⁻⁸ to 1×10⁻⁶ wt %.

Especially preferred are cationic textile softening compounds that arewater-insoluble quaternary ammonium materials having two C₁₂₋₂₂ alkyl oralkenyl groups connected to the molecule via at least one ester link,preferably two ester links. An especially preferred ester-linkedquaternary ammonium material can be represented by the formula III:

wherein each R₁ group is independently selected from C₁₋₄ alkyl orhydroxyalkyl groups or C₂₋₄ alkenyl groups; each R₂ group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; and whereinR₃ is a linear or branched alkylene group of 1 to 5 carbon atoms, T is

and p is 0 or is an integer from 1 to 5.

Di(tallowoxyloxyethyl) dimethyl ammonium chloride and/or its hardenedtallow analogue is especially preferred of the compounds of formula(II).

A second preferred type of quaternary ammonium material can berepresented by the formula (IV):

wherein R₁, p and R₂ are as defined above.

It is advantageous if the quaternary ammonium material is biologicallybiodegradable.

Preferred materials of this class such as 1,2-bis(hardenedtallowoyloxy)-3-trimethylammonium propane chloride and their methods ofpreparation are, for example, described in U.S. Pat. No. 4,137,180(Lever Brothers Co). Preferably these materials comprise small amountsof the corresponding monoester as described in U.S. Pat. No. 4,137,180,for example, 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammoniumpropane chloride.

Other useful cationic softening agents are alkyl pyridinium salts andsubstituted imidazoline species. Also useful are primary, secondary andtertiary amines and the condensation products of fatty acids withalkylpolyamines.

The compositions may alternatively or additionally contain water-solublecationic textile softeners, as described in GB 2 039 556B (Unilever).

The compositions may comprise a cationic textile softening compound andan oil, for example as disclosed in EP-A-0829531.

The compositions may alternatively or additionally contain nonionictextile softening agents such as lanolin and derivatives thereof.

Lecithins are also suitable softening compounds.

Nonionic softeners include Lβ phase forming sugar esters (as describedin M Hato et al Langmuir 12, 1659, 1666, (1996)) and related materialssuch as glycerol monostearate or sorbitan esters. Often these materialsare used in conjunction with cationic materials to assist deposition(see, for example, GB 2 202 244). Silicones are used in a similar way asa co-softener with a cationic softener in rinse treatments (see, forexample, GB 1 549 180).

The compositions may also suitably contain a nonionic stabilising agent.Suitable nonionic stabilising agents are linear C₈ to C₂₂ alcoholsalkoxylated with 10 to 20 moles of alkylene oxide, C₁₀ to C₂₀ alcohols,or mixtures thereof.

Advantageously the nonionic stabilising agent is a linear C₈ to C₂₂alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably,the level of nonionic stabiliser is within the range from 0.1 to 10% byweight, more preferably from 0.5 to 5% by weight, most preferably from 1to 4% by weight. The mole ratio of the quaternary ammonium compoundand/or other cationic softening agent to the nonionic stabilising agentis suitably within the range from 40:1 to about 1:1, preferably withinthe range from 18:1 to about 3:1.

The composition can also contain fatty acids, for example C₈ to C₂₄alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferablysaturated fatty acids are used, in particular, hardened tallow C₁₆ toC₁₈ fatty acids. Preferably the fatty acid is non-saponified, morepreferably the fatty acid is free, for example oleic acid, lauric acidor tallow fatty acid. The level of fatty acid material is preferablymore than 0.1% by weight, more preferably more than 0.2% by weight.Concentrated compositions may comprise from 0.5 to 20% by weight offatty acid, more preferably 1% to 10% by weight. The weight ratio ofquaternary ammonium material or other cationic softening agent to fattyacid material is preferably from 10:1 to 1:10.

Textile Treatment Product Forms

The composition of the invention may be in the form of a liquid, solid(e.g. powder or tablet), a gel or paste, spray, stick or a foam ormousse. Examples include a soaking product, a rinse treatment (e.g.conditioner or finisher) or a main-wash product. The composition mayalso be applied to a substrate e.g. a flexible sheet or used in adispenser which can be used in the wash cycle, rinse cycle or during thedryer cycle.

Liquid compositions may also include an agent which produces apearlescent appearance, e.g. an organic pearlising compound such asethylene glycol distearate, or inorganic pearlising pigments such asmicrofine mica or titanium dioxide (TiO₂) coated mica.

Liquid compositions may be in the form of emulsions or emulsionprecursors thereof.

The composition of the invention may further comprise a siliconecomponent. It is preferred if the silicone component is adimethylpolysiloxane with amino alkyl groups. It may be used in thecontext of the present invention as an emulsion in water.

It is preferred if the silicone component is present in a ratio of firstcomponent: silicone of from 1:1 to 30:1, preferably 1:1 to 20:1, morepreferably 2:1 to 20:1 and most preferably 5:1 to 15:1.

Silicone suitable for use in textile conditioning compositions includepredominately linear polydialkylsiloxanes, e.g. polydimethylsiloxanes oraminosilicones containing amine-functionalised side chains.

Composition may comprise soil release polymers such as block copolymersof polyethylene oxide and terephthalate.

Other optional ingredients include emulsifiers, electrolytes (forexample, sodium chloride or calcium chloride) preferably in the rangefrom 0.01 to.5% by weight, pH buffering agents, and perfumes (preferablyfrom 0.1 to 5% by weight).

Further optional ingredients include non-aqueous solvents, perfumecarriers, fluorescers, colourants, hydrotropes, antifoaming agents,antiredeposition agents, enzymes, optical brightening agents,opacifiers, dye transfer inhibitors.

In addition, compositions may comprise one or more anti-spotting agents,germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavymetal sequestrants, chlorine scavengers, dye fixatives, anti-corrosionagents, drape imparting agents, antistatic agents and ironing aids. Thelists of optional components are not intended to be exhaustive.

The invention will now be described by way of example only and withreference to the following non-limiting examples.

EXAMPLES Example 1

Method of Preparation of Voranol Iso-thiouronium Compounds

Voranol CP3055 ™ (ex-Dow Chemicals) (29.4 g, 0.01 moles, mw 2940) wasdissolved in toluene 50 mls. To this was added 3-bromopropionic acid(4.95 g, 3.3 equivalents Aldrich) and p-toluene sulphonic acid (1 g) toact as an acid catalyst. The solution was stirred by means of a magneticfollower on a hot plate. The solution was refluxed with a Dean and Starkdistillation trap. After 1.5 hours no more water was seen to azeotropefrom the reaction vessel into the side arm. The reaction was stopped andallowed to cool.

The toluene/Voranol solution was shaken with solution of sodiumbicarbonate (10 g/l). This was repeated five times, until the solutionwas seen not to fizz from the evolution of carbon dioxide gas and thewater was at a neutral pH. The two phases were separated and the toluenewas removed from the Voranol compound by rotary evaporation. Afterdrying in vacuo over calcium chloride the yield was 29.28 g (theoreticalyield is 33.44 g). The losses were mainly due to the highly viscoussticky nature of the polymer which stuck to glass ware. A pale yellowliquid product was obtained. FT-IR analysis confirmed the presence of anester group by showing a new peak at 1737 cm⁻¹

The product from the previous step was dissolved in ethanol (50 mls). Tothis solution was added thiourea (2.28 g 0.03 m Aldrich). This solutionwas then refluxed for six hours and cooled. The product was not isolatedsince the thick viscous nature of the pure product made it verydifficult to handle.

Addition of the compound to an aqueous solution at a pH below 4 gave awater-soluble product. At pH above pH8, the product is converted fromthe isothiouronium to produce a thiol group. This step results in theprecipitation of the polymer and an opaque, cloudy solution wasobserved.

Addition of the compound to a solution containing an anionic compounde.g. sodium dodecyl sulphate under acidic conditions leads to theprecipitation of a white sticky mass.

The formation of a thiol was determined by the use of Ellmans reagent,which reacts with thiol compounds forming an orange coloured solution.The formation and use of Ellmans reagent is described in PracticalProtein Chemistry, A Darbre, Wiley Interscience, New York 1970.

Isolation of a small quantity of isothiouronium polymer for FT-IRanalysis confirmed the structure by the presence of new peakscorrelating to the structure of isothiouronium groups.

Example 2

Experimental Procedure to Show Effect on Fibre Damage

Experiments were performed with pigment-printed, woven, cotton, red andblack, striped cloth. This was laundered in an unmodified AEG Lavamat50700 ™ washing machine on a cotton cycle at 40 Celsius. Theisothiouronium compound prepared according to the method described inexample 1 was introduced during the rinse cycle. After laundering, thesamples were dried at 50 Celsius in a fan oven for 20 minutes.

Samples which had been laundered up to five times were shown to a panelof independent observers for assessment of damage. Samples were observedin a light cabinet under D65 illumination. All of the observers were ofthe opinion that samples treated according to the method of theinvention were less damaged than controls. Damage was also measuredusing the gray scale measurement as detailed in BS1006/A02:1990. Resultswere as given below in Table 1.

From Table 1 it can be seen that there is a significant reduction in thelevel of damage as assessed by this method for embodiments of theinvention.

The least damage occurred when the protected thiol (isothiouronium)polymers were used together with azetidinium-containing polymers.

TABLE 1 Grey scale ratings for repeated washings of cloth with controland according to an embodiment of the method of the invention. Wash WashWash Wash Wash Treatment 1 2 3 4 5 Untreated 3 2–3 2–3 2 2 0.5% Voranolisothiouronium 3–4 3–4 3–4 3 3 (Ex. 1) 1.0% Voranol isothiouronium 3–43–4 3–4 3–4 3 (Ex. 1) 0.5% Voranol isothiouronium 4–5 4–5 4 4 4(Ex. 1) + 0.5% Listrilan azetidinium 1.0% Voranol isothiouronium 4–5 4–54–5 4–5 4 (Ex. 1) + 1.0% Listrilan azetidinium

1. A process for the laundering of non-keratinaceous textiles, whichcomprises the step of laundering the textiles with a compositioncomprising: a) a self-crosslinking cationic polymer; b) a nucleophilicspecies capable of reacting with polymer; c) a textile compatiblecarrier; d) wherein the nucleophilic species comprises a protectinggroup which is sufficiently labile that it leaves when the polymer andthe laundered textiles are exposed to a pH of above 8 at a temperatureof below 50 Celsius; and e) wherein the composition comprises adetergent active compound in the concentration of 5 to 50 wt. %.
 2. Aprocess according to claim 1, wherein the textile comprises cotton orregenerated cellulose.
 3. A process according to claim 1, wherein thecomposition further comprises a textile softening and/or conditioningcompound.
 4. A process according to claim 1 wherein the nucleophile is apolymer comprising at least one protected thiol group, wherein theprotecting group is labile under domestic washing conditions.
 5. Aprocess according to claim 4, wherein the protected thiol comprises aterminal or mid chain isothiouronium group.
 6. A process according toclaim 1 wherein the nucleophile is present in the composition in anamount such that from 0.0005% to 5% by weight on weight of textile isprovided.
 7. A process according to claim 1 wherein theself-crosslinking cationic polymer comprises a polymer havingazetidinium groups and/or one or more functional groups capable offorming azetidinium groups.
 8. A process according to claim 7 whereinthe composition comprises an amine or amide-epichlorohydrin resin havingone or more azetidinium functional groups.
 9. A process as claimed inclaim 1, wherein the composition is applied to the textile during therinse cycle of the laundering process.
 10. A detergent composition foruse in the process of claim 1 characterized in that the compositioncomprises: a) a self-crosslinking cationic polymer; b) a nucleophilicspecies capable of reacting with polymer (a); c) a textile compatiblecarrier; d) wherein the nucleophilic species comprises a protectinggroup which is sufficiently labile that it leaves when the polymer andthe laundered textiles are exposed to a pH of above 8 at a temperatureof below 50 Celsius; and e) wherein the composition comprises adetergent active compound in the concentration range of 5 to 50 wt. %.